CN1980736B - A sol comprising hybrid transition metal oxide nanoparticles - Google Patents
A sol comprising hybrid transition metal oxide nanoparticles Download PDFInfo
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- CN1980736B CN1980736B CN2005800205123A CN200580020512A CN1980736B CN 1980736 B CN1980736 B CN 1980736B CN 2005800205123 A CN2005800205123 A CN 2005800205123A CN 200580020512 A CN200580020512 A CN 200580020512A CN 1980736 B CN1980736 B CN 1980736B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 23
- 229910000314 transition metal oxide Inorganic materials 0.000 title description 2
- 239000002184 metal Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 239000010948 rhodium Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 42
- 239000002585 base Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000012876 carrier material Substances 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001935 peptisation Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- -1 organic acid anion Chemical class 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 16
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004125 X-ray microanalysis Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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Abstract
A sol comprising metal oxide nanoparticles dispersed in an aqueous liquid, and further comprising stabiliser ions is disclosed. The metal oxide particles comprise one or more metals selected from a first group consisting of cerium, zirconium, iron, manganese and titanium, and one or more metals selected from a second group consisting of platinum, palladium, rhodium, ruthenium, iridium and osmium. The sols can be used to deposit catalytic coatings onto catalyst substrates, including substrates with narrow channels (i.e. channels with a diameter of less than 500 m).
Description
The present invention relates to metal oxide sol.The invention further relates to the method for using this metal oxide sol coated catalysts base material.
Platinum group metal (platinum, palladium, rhodium, iridium, ruthenium and osmium) is usually used in the catalysis occasion.Catalytic reaction is carried out on metallic surface, therefore usually will be by making the long-pending maximization of metallic surface on the surface that short grained metal is dispersed in carrier material.Carrier material normally oxide material and can be by metal-carrier interact (MSI) change the sense oxide material of metal catalytic activity.Contact with carrier material by slaine wherein and to make catalyst precarsor be adsorbed to the technology on the carrier, metal can deposit on the carrier material.Carrier material is heated to high temperature so that the metal of precursors decompose catalytic activity form.
For many occasions, catalyst is deposited to flow-through substrate such as material all in one piece, foamed material, static mixer or heat exchanger unit.Carrier material can be deposited on the base material and also subsequently the platinum group metal be deposited on the carrier material.In addition, the platinum group metal can be deposited on the carrier material and the catalytic carrier material can be deposited on the base material subsequently.
Need to reduce the size of the passage in the flow-through substrate.Smaller channels can increase the internal surface area of base material under given substrate sizes, or can keep surface area when reducing substrate sizes.But be difficult to be coated to catalyst material on the wall of passage aisle and the size of the passage size restrictions of suppressed by vector material effectively.
The inventor seeks to provide a kind of catalyst (comprising platinum group metal and function metal oxide) is coated to the method on the base material, and wherein this method is applicable to and applies the base material with narrow passage (being lower than 500 μ m).The inventor has developed and can be used for catalytic coatings is deposited to colloidal sol on the base material.Colloidal sol is the aqueous colloidal dispersion of solid particle in liquid.Colloidal sol of the present invention is stable and can stores the several months before being used for coated substrate.Colloidal sol of the present invention is different from " colloidal sol " made that is usually used in preparing catalyst in the sol-gel technology process.In sol-gel technology, purpose is not to produce the stable sols that can store and use subsequently, also further transforms so that gel to be provided but produce colloidal sol, and the latter further transforms so that solid to be provided.
The invention provides a kind of colloidal sol that is dispersed in the metal oxide nanoparticles in liquid, aqueous that comprises, wherein each metal oxide nanoparticles comprises one or more and is selected from by cerium zirconium, iron, first group the metal that manganese and titanium are formed, be selected from by platinum palladium, rhodium with one or more, ruthenium, second group the metal that iridium and osmium are formed, wherein one or more metals that are selected from first group fully mix with one or more metals that are selected from second group and wherein colloidal sol further comprise stabilizer ions.
Each metal oxide nanoparticles comprises one or more function metal oxide materials: ceria, zirconia, iron oxide, manganese oxide and/or titanium dioxide.Each nano particle further comprises one or more platinums group metal that can be used as oxide or exist as metal.The function metal oxide fully contacts with the platinum group metal and fully mixes, and it is believed that like this provides the good metal carrier to interact.
WO 00/27527 discloses a kind of method that forms bearing catalyst, and wherein ceria nano particle and zirconium and platinum salt are dispersed in the water.Platinum-ceria-zirconia catalyst is dispersed on the gamma-aluminium oxide carrier material subsequently.The author claims that platinum is dispersed on the surface of ceria-zirconium oxide nano crystal body.On the contrary, in the nano particle of colloidal sol of the present invention, one or more metals that are selected from first group fully mix with the metal that one or more are selected from second group.Term " fully mixing " is meant that one or more metals and one or more metals that are selected from second group that are selected from first group are dispersed in the whole nano particle.This can be by confirming as the technology of high-resolution transmission microscopy method and in conjunction with the x-ray microanalysis.
Preferably, one or more metals that are selected from first group are that cerium or cerium and zirconium and one or more metals that is selected from second group are platinum and/or rhodium, most preferably platinum.
Except being selected from the oxide of first and second groups metal, metal oxide nanoparticles can comprise other metal oxide.Other metal oxide can improve the adhesiveness of nano particle and base material, maybe can reduce the amount of the expensive components in the nano particle and not detailed reduction catalytic effect.Preferably other metal oxide is an aluminium oxide.Preferably, all metal oxides in the nano particle fully mix.
One or more mol ratios that are selected from first group metal and one or more metals that are selected from second group suitably at least 1, preferably at least 5 and most preferably at least 10.Being lower than 1 ratio provides the platinum group metal of larger proportion, therefore uneconomical and often can not improve catalytic effect.
Metal: the mol ratio of stabilizer ions suitably at least 0.7 and preferably at least 1.In this ratio, " metal " is the molal quantity of the metal ion in the oxide nano particles, comprises first group, second group metal and any other metal.The stabilizer ions of low content means that this colloidal sol is advantageously used in the carrier material of preparation catalysis.Stabilizer ions removes (with therefore catalyst property is unaffected) by K cryogenic treatment easily and the environmental impact of stabilizing agent removal is minimized.
Metal oxide nanoparticles has the average diameter that is lower than 10nm suitably and preferably has the average diameter that is lower than 5nm.Colloidal sol can be advantageously used in and apply the base material with narrow passage (diameter is lower than 500 μ m).
Stabilizer ions is anion and be preferably the anion of inorganic acid suitably, and as nitrate ion, or pKa (with respect to water) is lower than 8 organic acid anion, as acetate ion.
The concentration of metal oxide nanoparticles in colloidal sol is 50g/l at least suitably, preferably 100g/l and most preferably 200g/l at least at least.
The present invention further provides a kind of method that is used to prepare according to colloidal sol of the present invention, this method may further comprise the steps:
A) aqueous solution of preparation slaine, wherein slaine comprises one or more and is selected from by cerium, zirconium, iron, first group the metal that manganese and titanium are formed and one or more are selected from by platinum, palladium, rhodium, ruthenium, second group the metal that iridium and osmium are formed;
B) aqueous solution slaine is added in the alkali to form the precipitation of hydroxide thing; With
C) acid is added the precipitation of hydroxide thing so that this sediment peptization and forming by this sour conjugate base stable sols.
Preferably, slaine is a metal nitrate.The aqueous solution is mixed suitably and join in alkali such as the ammonia, and the precipitation of hydroxide thing is provided.Sediment is filtered suitably and fully washs to remove any remaining salt.The precipitation of hydroxide thing is subsequently by providing the sour peptization of stabilizer ions.If stabilizer ions is the anion of inorganic acid, peptizing agent is an inorganic acid so.
The present invention further provides a kind of method, colloidal sol wherein of the present invention is used for the coated catalysts base material.Base material can be standard catalyst base material such as material all in one piece, foamed material, and filter or catalyst pellets and base material can be used high surface area support material such as aluminium oxide precoating.But in embodiment preferred of the present invention, base material is to have the narrow passage that is used to transmit reactant and product, and promptly diameter is lower than the passage of 500 μ m and any catalyst substrate that preferred diameter is lower than the passage of 200 μ m.An example of this base material is the so-called microreactor that comprises etch plate.Colloidal sol of the present invention is advantageously used in and applies the base material with very thin passage, because metal oxide nanoparticles little (having the average diameter that is lower than 10nm suitably) and be not difficult to make nano particle by passage and they are deposited on the conduit wall.On the contrary, the conventional washing paint-on technique can not be used to apply the wherein narrow catalyst substrate of passage, because washing applies slurry meeting blocking channel.
In another embodiment preferred, colloidal sol of the present invention is used for the coated catalysts base material, and wherein base material is a catalyst pellets.The inventor has been found that colloidal sol of the present invention can be used for preparing the catalysis pellet, and wherein catalyst permeates by pellet and is keyed on the pellet securely.
In first embodiment of this method, colloidal sol is by contacting colloidal sol and directly be coated on the base material with base material.This method is applicable to and applies all catalyst substrate, comprises the catalyst substrate with narrow (diameter is lower than 500 μ m) passage and comprises catalyst pellets.Preferably, the viscosity of colloidal sol increases by adding viscosity modifier such as hydroxyethylcellulose in colloidal sol.Colloidal sol can be applied on the channelled base material by using vacuum to make colloidal sol pass the base material passage.At colloidal sol with after base material contacts, with base material drying (as under 130 ℃) and calcining (as under 500 ℃).
In second embodiment of this method, colloidal sol is initial to be coated on carrier material such as metal oxide materials or the material with carbon element forming the catalytic carrier material, and subsequently the catalytic carrier material is deposited on the catalyst substrate.This method not too is applicable to apply to have the catalyst substrate of thin passage.Suitable metal oxide materials often has greater than 50m
2The surface area of/g and be preferably selected from aluminium, silicon, magnesium, titanium, cerium, zirconium, the oxide of iron and tin and mixed oxide.Suitable material with carbon element comprises carbon black, graphite and active carbon.
In order to prepare the bearing catalyst material, can use dipping method, wherein colloidal sol contacts with the carrier material of powder type.Suitably, powder and colloidal sol mix, and filter and are being no more than 200 ℃ suitably, and is dry under preferred about 100 ℃ temperature.In addition, can use absorption process, wherein colloidal sol is added in the aqueous slurries that comprises carrier material particles.Suitably slurry and colloidal sol are mixed, filter and be no more than 200 ℃ suitably, dry under preferred about 100 ℃ temperature.The bearing catalyst material can use the technology that those skilled in the art know and deposit on the catalyst substrate.
The present invention is existing to be described by embodiment, but these embodiment are used for explanation and non-limiting the present invention.
Embodiment 1: by the Pt/CeO that comprises of nitrate ion stabilisation
2/ ZrO
2/ Al
2O
3Colloidal sol
(from Johnson Matthey (UK), 3.05g 16.37%Pt) joins and comprises cerous nitrate (IV) (45ml comprises 18.8g/0.109mol CeO with platinum nitrate (IV)
2Equivalent), (16.3ml comprises 4.5g/0.037mol ZrO to zirconium nitrate
2Equivalent) and in the aqueous solution of aluminum nitrate (9.04g/0.024mol).Solution is added ammonia (200ml 4M) and forms sediment.Sediment reclaimed and wash with water by filtration until sedimentary electrical conductivity be lower than 100 μ S, show that most remaining nitrate is removed.Filter cake with nitric acid (1M) peptization, is obtained having oxide content 100gl
-1Colloidal sol.Metal in the colloidal sol (platinum, cerium, zirconium and aluminium) is 1: 1 with the ratio of nitrate ion.Platinum: cerium: zirconium: the ratio of aluminium is 1: 42.6: 14.5: 9.4.
Embodiment 2: by the Pt/Rh/CeO that comprises of nitrate ion stabilisation
2/ ZrO
2/ Al
2O
3Colloidal sol
With platinum nitrate (IV) (from Johnson Matthey (UK), 3.05g, 16.37%Pt) and rhodium nitrate (from Johnson Matthey (UK), 1.79g 13.93%Rh) joins and comprises cerous nitrate (IV) (45ml comprises 18.6g/0.108mol CeO
2Equivalent), (16.2ml comprises 4.4g/0.036mol ZrO to zirconium nitrate
2Equivalent) and in the aqueous solution of aluminum nitrate (9.04g/0.024mol).Solution is added ammonia (200ml 4M) and forms sediment.Sediment reclaimed and wash with water by filtration until sedimentary electrical conductivity be lower than 100 μ S, show that most remaining nitrate is removed.Filter cake with nitric acid (1M) peptization, is obtained having oxide content 200gl
-1Colloidal sol.Metal in the colloidal sol (platinum, rhodium, cerium, zirconium and aluminium) is 1: 1 with the ratio of nitrate ion.Platinum: rhodium: cerium: zirconium: the ratio of aluminium is 1: 1: 42.4: 14.1: 9.4.
Embodiment 3: by the Pt/CeO that comprises of nitrate ion stabilisation
2/ ZrO
2Colloidal sol
(from Johnson Matthey (UK), 1.53g 16.37%Pt) joins and comprises cerous nitrate (IV) (28ml comprises 10.0g/0.058mol CeO with platinum nitrate (IV)
2Equivalent) and zirconium nitrate (8.6ml comprises 2.4g/0.019mol ZrO
2Equivalent) in the aqueous solution.Solution is added ammonia (100ml 4M) and forms sediment.Sediment reclaimed and wash with water by filtration until sedimentary electrical conductivity be lower than 100 μ S, show that most remaining nitrate is removed.Filter cake with nitric acid (1M) peptization, is obtained having oxide content 90gl
-1Colloidal sol. the ratio of the metal in the colloidal sol (platinum, cerium and zirconium) and nitrate ion is 1: 1. platinum: cerium: the ratio of zirconium is 1: 45.3: 14.8.
Embodiment 4: by the Rh/CeO that comprises of nitrate ion stabilisation
2/ ZrO
2Colloidal sol
Prepare in 200ml water, comprise rhodium nitrate (from Johnson Matthey (UK), 3.59g, 13.93%Rh), (47.8ml comprises 19.8g/0.11mol CeO to cerous nitrate (IV)
2Equivalent) and zirconium nitrate (12.7ml comprises 3.5g/0.03mol ZrO
2Equivalent) solution.Under agitation this aqueous solution is dropped to 4M ammonia solution (200ml).Form sediment and reclaim by filtration.Sediment is washed with water to remove remaining nitrate.Filter cake is by adding nitric acid (1M) and adding thermal agitation 2-3 hour and peptization under 80 ℃.Obtain colloidal sol oxide content 197gl like this
-1Colloidal sol.Metal in the colloidal sol (rhodium, cerium and zirconium) is 2: 1 with the ratio of nitrate ion.
Embodiment 5: by the Rh/CeO that comprises of nitrate ion stabilisation
2/ ZrO
2/ Al
2O
3Colloidal sol
Prepare in 200ml water, comprise rhodium nitrate (from Johnson Matthey (UK), 3.59g, 13.93%Rh), (47.8ml comprises 19.8g/0.11mol CeO to cerous nitrate (IV)
2Equivalent), (12.7ml comprises 3.5g/0.03mol ZrO to zirconium nitrate
2Equivalent) and the solution of aluminum nitrate (9.19g comprises 0.0245mol).This aqueous solution is under agitation dropped to 4M ammonia solution (200ml).Form sediment and reclaim by filtration.Sediment is washed with water to remove remaining nitrate.Filter cake is by adding nitric acid (1M) and adding thermal agitation 2-3 hour and peptization under 80 ℃.Metal in the colloidal sol (rhodium, cerium, zirconium and aluminium) is 5: 3 with the ratio of nitrate ion.
Embodiment 6: apply microreactor
The colloidal sol of making according to embodiment 1 is by the value 0.9 during from preparation is adjusted to 3 and add 0.5wt%Natrosol with pH with 1M ammonia
TMHydroxyethylcellulose and thickening.Natrosol dissolved in about 3 hours, obtained the rubber-like solution of thickness.Colloidal sol is coated to comprises etch silicon plate and having on the microreactor of the channel size that is lower than 200 μ m.Thickening colloidal sol is passed through this microreactor under vacuum, at microreactor inside deposition one deck colloidal sol.Reactor is 130 ℃ of dry down and calcinings under 500 ℃.
Embodiment 7: the coated catalysts pellet
The Alpha-alumina catalyst pellets is immersed in the colloidal sol of making according to embodiment 45 minutes.Pellet is taken out from colloidal sol, and use compressed air that excessive colloidal sol is removed from pellet.Pellet was calcined 2 hours down 120 ℃ of following dryings 8 hours with at 500 ℃.This technology repeats 3 times.
Afterwards, the weight of pellet increases by 3.9% in primary coating step only (being immersed in the colloidal sol drying, calcining); After twice coating step, the weight increase be 7.7% and after three coating steps the weight increase be 10.9%.
Embodiment 7: the coated catalysts pellet
The Alpha-alumina catalyst pellets is immersed in the colloidal sol of making according to embodiment 45 minutes.Pellet is taken out from colloidal sol, and use compressed air that excessive colloidal sol is removed from pellet.Pellet was calcined 2 hours down 120 ℃ of following dryings 8 hours with at 500 ℃.After this technology, the average weight value added of pellet is 3.7%.
Claims (12)
1. one kind comprises the colloidal sol that is dispersed in the metal oxide nanoparticles in liquid, aqueous, wherein each metal oxide nanoparticles comprises one or more and is selected from by cerium, zirconium, iron, first group the metal that manganese and titanium are formed, one or more are selected from by platinum, palladium, rhodium, ruthenium, second group metal and aluminium oxide that iridium and osmium are formed, wherein one or more metals that are selected from first group fully mix with metal and the aluminium oxide that one or more are selected from second group, and wherein this colloidal sol further comprises stabilizer ions, and the concentration of metal oxide nanoparticles in colloidal sol is 50g/l at least.
2. the colloidal sol of claim 1, wherein one or more metals that are selected from first group are cerium or cerium and zirconium, and one or more metals that are selected from second group are platinum and/or rhodium.
3. the colloidal sol of claim 1 or claim 2, wherein one or more metal and one or more mol ratios that are selected from second group metal that are selected from first group are at least 1.
4. the colloidal sol of claim 3, wherein one or more metal and one or more mol ratios that are selected from second group metal that are selected from first group are at least 10.
5. the colloidal sol of claim 1 or claim 2, wherein metal: the mol ratio of stabilizer ions is at least 0.7.
6. the colloidal sol of claim 1 or claim 2, wherein metal oxide nanoparticles has the average diameter that is lower than 10nm.
7. the colloidal sol of claim 1 or claim 2, wherein stabilizer ions is the anion of inorganic acid or is lower than 8 organic acid anion with respect to the pKa of water.
8. method that is used to prepare the colloidal sol of claim 1 or claim 2, this method may further comprise the steps:
A) aqueous solution of preparation slaine, wherein slaine comprises aluminium and one or more and is selected from by cerium, zirconium, iron, first group the metal that manganese and titanium are formed and one or more are selected from by platinum, palladium, rhodium, ruthenium, second group the metal that iridium and osmium are formed;
B) alkali is added the aqueous solution of slaine to form the precipitation of hydroxide thing; With
C) acid is added the precipitation of hydroxide thing so that sediment peptization and forming by this sour conjugate base stable sols.
9. the method for a coated catalysts base material wherein makes the colloidal sol of method preparation claim 1 or claim 2 or according to Claim 8 contact with catalyst substrate.
10. the method for claim 9, wherein catalyst substrate has the passage that diameter is lower than 500 μ m.
11. the method for claim 9, wherein catalyst substrate is a catalyst pellets.
12. the method for a coated catalysts base material, wherein the colloidal sol of method claim 1 or claim 2 or according to Claim 8 preparation is coated on the carrier material forming the catalytic carrier material, and the catalytic carrier material is deposited on the catalyst substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0413767.5A GB0413767D0 (en) | 2004-06-21 | 2004-06-21 | Metal oxide sols |
| GB0413767.5 | 2004-06-21 | ||
| PCT/GB2005/002382 WO2005123594A2 (en) | 2004-06-21 | 2005-06-17 | Sols comprising mixed transitional metal oxide nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1980736A CN1980736A (en) | 2007-06-13 |
| CN1980736B true CN1980736B (en) | 2010-05-05 |
Family
ID=32750236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800205123A Expired - Fee Related CN1980736B (en) | 2004-06-21 | 2005-06-17 | A sol comprising hybrid transition metal oxide nanoparticles |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8173572B2 (en) |
| EP (1) | EP1758821A2 (en) |
| CN (1) | CN1980736B (en) |
| GB (1) | GB0413767D0 (en) |
| WO (1) | WO2005123594A2 (en) |
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| GB0413771D0 (en) * | 2004-06-21 | 2004-07-21 | Johnson Matthey Plc | Metal oxide sols |
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| EP2027371B1 (en) * | 2006-06-15 | 2019-12-04 | Dinex Finland Oy | Coating for particulate filters |
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| US9291082B2 (en) * | 2012-09-26 | 2016-03-22 | General Electric Company | System and method of a catalytic reactor having multiple sacrificial coatings |
| US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
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| CN105592921A (en) | 2013-07-25 | 2016-05-18 | Sdc材料公司 | Washcoats and coated substrates for catalytic converters and method for manufacturing and using same |
| CN106061600A (en) | 2013-10-22 | 2016-10-26 | Sdc材料公司 | Catalyst design for heavy-duty diesel combustion engines |
| EP3068517A4 (en) | 2013-10-22 | 2017-07-05 | SDCMaterials, Inc. | Compositions of lean nox trap |
| EP3119500A4 (en) | 2014-03-21 | 2017-12-13 | SDC Materials, Inc. | Compositions for passive nox adsorption (pna) systems |
| EP3419754B1 (en) * | 2016-02-24 | 2020-08-26 | Haldor Topsøe A/S | Method for the preparation of a zone coated catalysed monolith |
| US10195602B2 (en) * | 2016-12-01 | 2019-02-05 | GM Global Technology Operations LLC | Nucleation layers for enhancing photocatalytic activity of titanium dioxide (TiO2) coatings |
| CN114618400B (en) * | 2020-12-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Preparation method and application of cerium-zirconium sol |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1980736A (en) | 2007-06-13 |
| US20110160050A1 (en) | 2011-06-30 |
| US8173572B2 (en) | 2012-05-08 |
| GB0413767D0 (en) | 2004-07-21 |
| WO2005123594A2 (en) | 2005-12-29 |
| WO2005123594A3 (en) | 2006-03-16 |
| EP1758821A2 (en) | 2007-03-07 |
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